Method for coloring fibrous material composed of phenolic resins

ABSTRACT

A method for coloring fibers or fibrous structures composed of phenolic resins, which comprises applying a dye liquor to the fibers or fibrous structures, and then contacting them with a vapor of at least one compound selected from the group consisting of N,N-dialkyl acetylamides, dialkyl sulfoxides, ketones, alcohols, aliphatic amines and dioxane, or a mixed vapor of such compound and water.

United States Patent 1 1 1 Dec. 23, 1975 10/1950 Koberlein 8/169 X lda et al.

[ METHOD FOR COLORING FIBROUS 3,519,371 1/1970 Kitamura et al. 8/172 x MATERI L COMPOSED 0 PHENOLIC 3,606,988 9/1971 Wa1z et a1 8/172 X RESINS 3,667,898 6/1972 Bergman et a1 8/172 X 3,716,521 2/1973 Economy et a1. 264/176 F X [75] Inventors: Syunya Ida, Nara; Norio Endo, 3,723,558 3/1973 Kramer 264/176 F X Osaka, both of Japan [73] Assignee: Kaneho, Ltd., Tokyo, Japan Primary ExaminerVerlin R. Pendegrass Assistant Examiner-P. A. Nelson [22] filed 1973 Attorney, Agent, or Firm-Sherman &. Shalloway [21] Appl. No.: 351,884

301 Foreign Application Priority Data [57] 38mm A r. 20, 1972 Japan 47-40115 A method for coloring fibers or fibrous structures composed of phenolic resins, which comprises apply [52] US. Cl. 8/173; 8/174; 8/93 ing a dye liquor to the fibers or fibrous structures, and

[51] Int. Cl. D061 5/04 then contacting them with a vapor of at least one com- [58] Field ofSearch 8/172, 173, 174, 93; pound selected from the group consisting of N,N-

264/ 176 F dialkyl acetylamides, dialkyl sulfoxides, ketones, alcohols, aliphatic amines and dioxane, or a mixed vapor 6] References Cited of such compound and water.

UNITED STATES PATENTS 7 Claims, No Drawings METHOD FOR COLORING FIBROUS MATERIAL COMPOSED OF PHENOLIC RESINS This invention relates to a method for coloring fibers or fibrous structures prepared from phenolic resins. More specifically, this invention relates to a method for uniformly coloring phenolic fibers or their structures in deep fast colors.

As is well known, fibers composed of phenolic resins (to be referred to simply as phenolic fibers) have poor affinity with dyes and extremely low dyeability for a variety of reasons such as their compact fibrous structure, the lack of dye-affinitive groups, or their high negative surface potential. It is very difficult therefore to color phenolic fibers uniformly in deep fast colors.

Other fibers having a compact fibrous structure and no dye-affinitive groups, such as polyester fibers or polypropylene fibers, are colored at a temperature as high as 1 to 130C. using dyes having a small molecular volume, or using a dye liquor containing a carrier material (swelling agent) such as ortho-phenylphenol, chlorobenzene, a salicylic acid ester or a benzoic acid ester in order to give satisfactory dyeings.

in contrast, the phenolic fibers can scarcely be colored substantially even at 1 10 to 130C. using a carrier material such as those mentioned above, and it has been difficult to provide colored phenolic fibers which are useful for practical applications.

Certain kinds of such difficulty-dyeable synthetic fibers have previously been colored, for example, by a method wherein a substance having dye-affinitive groups, such as a polymer having a free amino group, is incorporated in a spinning solution, and fibers obtained by spinning this solution are dyed by conventional methods, a method wherein a pigment is incorporated in a spinning solution beforehand, and the spinning solution is spun to form colored fibers, or a method wherein a pigment is fixed to the surface of the fibers by a binder to color the fibers are also known.

However, when such methods are used for coloring phenolic fibers, the results are poor. For example, when a reagent (for example, hydrazine) having a functional group capable of being bound to a dye or an organic or inorganic pigment is added to a molten prepolymer of the phenol type, and the mixture is spun and then cured, the tenacity of the phenolic fibers after curing is markedly reduced, or the desirable non-combustibility of phenolic fibers is impaired. On the other hand, when the phenolic fibers are colored by fixing a pigment to their surfaces using a binder, the resulting colored fibers prove infeasible because of poor fastness characteristics or harsh finish. In addition, many binders that can be applied for this purpose impart combustibility to the phenolic fibers, and thus hamper their most desirable property (i.e., non-combustibility).

Alternatively, wool, cellulosic fibers or polyamide synthetic fibers are dyed by a method wherein a dye liquor is uniformly applied to the fibers and then the fibers are treated with saturated or superheated steam, a method wherein the fibers are likewise treated with steam containing an acid, or a method wherein the fibers are treated with a vapor of water containing an aromatic or alicyclic compound such as phenol, ophenylphenol, ochloropheno1, B-naphthol, m-cresol, cyclohexanol, aniline, N-methylaniline, N-dimethylaniline, N-ethylaniline, or N-diethylaniline.

However, even if the above steaming methods are applied to the dyeing of phenolic fibrous materials, for example, by steaming the fibrous materials with saturated steam under pressure at a temperature higher than C. or with a mixed vapor of the aromatic or alicyclic compound, they cannot be dyed even in a light color.

Thus, the conventional methods for coloring synthetic fibers have not proved satisfactory for coloring phenolic fibers, and the development of a dyeing method for the phenolic fibers which can gain commercial acceptance with good results has been strongly desired.

A primary object of this invention is to provide an improved method for coloring fibers composed of phenolic resins and their structures (to be referred to generically as phenolic fibrous materials).

A secondary object of this invention is to provide a method for uniformly coloring phenolic fibrous material in deep fast colors.

Another object of this invention is to provide a method for coloring phenolic fibrous materials that can be utilized industrially.

The above and other objects of this invention and the advantages of this invention will become apparent from the following description.

According to the present invention, there is provided a method for coloring fibers or fibrous structures composed of phenolic resins, which comprises applying a dye liquor to the fibers or fibrous structures, and then contacting them with a vapor of at least one compound selected from the group consisting of N,N-dialkyl acetylamides, dialkyl sulfoxides, ketones, alcohols, aliphatic amines and dioxane, or a mixed vapor of such compound and water.

The term fibers composed of phenolic resins (phenolic fibers), as referred to in the present specification and claims, denotes uncured fibers formed by melt spinning, or wet spinning, etc. of a prepolymer of the novolak or resol type prepared from a phenol (e.g., phenol, cresol, xylenol, ethylphenol, phenylphenol, amylphenol, bisphenol A, or resorcinol) and an aidehyde (formaldehyde, acetaldehyde, para-formaldehyde, hexamethylene tetramine, furfural, glutaraldehyde, or glyoxal), or the cured products thereof obtained by curing such uncured fibers with a curing agent such as an aldehyde in the presence of an alkaline or acidic catalyst.

Since the phenolic fibers can be produced by any known method, we will not describe it here.

The phenolic fibers to be dyed by the method of this invention may be composed of a phenolic resin alone, or a blend of a major proportion of the phenolic resin with a minor proportion (generally, 1-40% by weight) of another fiber-forming polymer. In order, however, not to impair the incombustibility of the phenolic resins the amount of the fiber-forming polymer should be as small as possible, preferably up to 30 by weight, when the blend is used, or the phenolic fibers should be composed solely of the phenolic resin.

Specific examples of the fiber-forming polymer that can be used include polyamide resins such as nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 61 1, nylon 612, and blends of two or more of these with each other; polyester resins such as polyethylene terephthalate, polyesters derived from the same constituent elements as polyethylene terephthalate with part of ethylene glycol replaced by other known glycols, polyesters derived from the same constituent elements as polyethylene terephthalate with the terephthalic acid replaced by orthoor metaphthalic acids, other known aliphatic dicarboxylic acids or blends of two or more of these with each other; polyester ethers such as polyethylene hydroxybenzoate, and polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymer, or blends of two or more of these with each other.

The term fibrous structures composed of phenolic resins used in the present specification and claims, denotes a fibrous product such as a web, yarn, woven fabric, knitted fabric, non-woven fabric, carpet, batt or laminated cloth composed of the phenolic fibers alone or a composite of the phenolic fibers and other natural, semisynthetic or synthetic fibers.

The coloring of these phenolic fibrous materials can be performed by the known methods usually employed to dye usual fibrous materials.

The term coloring (or dyeing), used in the present specification and claims, denotes coloring in a broad sense, and therefore, includes (a) the dip dyeing whereby a fibrous material is dyed as dipped in a dye solution, (b) the pad dyeing whereby a dye solution is padded on a fibrous material, and then the fibrous material is heated, and (c) the printing whereby a printing paste is applied to a fibrous material, and the material is then heated to color the printed portions.

Accordingly, the dye liquor used in accordance with the process of this invention may be in the form of a solution containing a dye (especially in the case of dip dyeing) or a paste containing a dye (pad dyeing and printing).

The application of a dye liquor to the phenolic fibrous materials by the pad dyeing or printing process can be effected, for example, by padding an aqueous dye solution containing about to 50 by weight, based on the material to be dyed, of a dye and if desired a small amount of a viscosity regulator, or by printing a paste-like dye liquor containing about 5 to 50 by weight, based on the weight of the fibrous material to be dyed, ofa dye, about 0.l l0 by weight, based on the total weight of the liquor, of a size, and water. After padding or printing, the fibrous material is treated with steam either as such or after drying.

Most of the dyes that are usually used in the dyeing of natural, semi-synthetic or synthetic fibrous materials can be used in accordance with the method of this invention for dyeing the phenolic fibrous materials. For example, there are used, vat dyes, azoic dyes, cationic dyes, disperse dyes, metal-containing dyes, acid dyes, direct dyes, reactive dyes, and chrome dyes. Of these, the azoic dyes, cationic dyes, disperse dyes and vat dyes have good dyeability with regard to the phenolic fibers, and can be conveniently used in the present inventioh. Typical examples of these dyes are as follows:

1. Cationic dyes Cationic dyes of the azo, diphenylmethane, triphenylmethane, xanthene, acridine, quinoline, methine, thiazole, azine, thiazine, and oxazine types. Specific examples are Sumiacryl Orange G (C.l. Basic Orange 2!), Sumiacryl Brilliant Red BB, Sumiacryl Red 68 (C.l. Basic Violet 7), Sumiacryl Brown (C.l. Basic Orange 30), Sumiacryl Blue 66 (C.l. Basic Blue 22), Diacryl Brilliant Pink R (C.l. Basic Red Diacryl Blue 2RL (C.l. Basic Blue 59), Diacryl Green 2BL' 4 (C.l. Basic Green 77), and Diacryl Violet BRL (C.l.

Basic Violet 26).

2. Disperse dyes Disperse dyes of the azo, anthraquinone, nitro, aminoquinone and methine types. Specific examples are Dianix Fast Orange R-FS, Dianix Fast Red B-FS, Dianix Red Brown R-FS, Kayalon Polyester Violet BNF (C.l. Disperse Violet 30), Kayalon Polyester Pink BSF (C.l. Disperse Red 55), Sumikalon Red FB (C.l. Disperse Red 60), Sumikalon Blue R (C.l. Disperse Blue 71 and Sumikalon Dark Blue RB (C.l. Disperse Blue 55).

3. Azoic dyes 4. Vat dyes Vat dyes of the anthraquinone and indigozoyl types. Specific examples are Caledon Orange Brown 26 (C.l. Vat Orange 14), Caledon Red B (C.l. Vat Red 41), Mikethrene Violet FFBN (C.l. Vat Violet l3) Nihonthrene Dark Blue BO (C.l. Vat Blue 20), Caledon Olive OMW (C.l. Vat Green 26), and lndanthrene Black Brown RV (C.l. Vat Brown 56).

Examples of the size to be incorporated in the dye liquor include starch, sodium alginate, tragacanth gum, gum arabic, gelatin, dextrin, British gum, carboxymethylcellulose, methyl cellulose, hydroxyethyl cellulose, carboxymethyl starch, polyvinyl alcohol, poly(- sodium acrylate), kerosene, and 1,l ,l-trichloroethane. Of these, kerosene and Lt .l-trichloroethane are especially suited for preparing an emulsion paste. These sizes can also be used as a viscosity regulator of the dye liquor. They, however, should not be dissolved at the time of steam treatment to destroy the printed pattern or should not be coagulated to make it difficult to remove them.

The phenolic fibrous material to which the dye liquor has been applied by any of the above-mentioned dyeing methods is treated with steam by the method of this invention either as such or after drying. Accordingly, the method of this invention has the advantage of being applicable also to the pad roll process.

The drying of the fibrous material before steam treatment is usually performed at a temperature of to l20C., preferably to C, although it differs according to the dyeing method used.

As previously described, the steaming treatment in accordance with this invention can be achieved by contacting the material, to which a dye liquor has been applied, with a vapor of at least one compound selected from the group consisting of N,N-dialkyl acrylamides, dialkyl sulfoxides, ketones, alcohols, aliphatic amines and dioxane or a mixed vapor of this compound with water.

The two alkyl moieties in the N,N-dialkyl acylarnides and the dialkyl sulfoxides are the same or different, and suitably a lower alkyl group containing 1 to 5 carbon atoms, such as a methyl or ethyl group. The acyl" is a residue of an acid, for example, a formyl, acetyl or propionyl group. Thus, the preferred N,N-dialkyl acylamides are N,N-dimethyl formamide, N,N-diethyl formamide, N,N-dimethyl acetamide, N,N-diethyl acetamide, and methylethyl N,N-acetamide. Dimethyl sulfoxide and diethyl sulfoxide are the preferred dialkyl sulfoxides.

The ketones that can be used in this invention are expressed by the formula wherein R and R, may be the same or different, and represent an alkyl group, preferably a lower alkyl group having 1 to carbon atoms, or a phenyl group, or R and R, together may form an alkylene group, especially a hexylene group. Examples of the ketones suitably used in this invention are acetone, diethyl ketone, methyl ethyl ketone, acetophenone, and cyclohexanone.

TheK alcigli lols are expressed by the formula wherein R, is an alkyl group, preferably a lower alkyl group having up to 4 carbon atoms, an aralkyl group such as a benzyl group, or a heterocyclic group such as a furfuryl or tetrahydrofurfuryl group. Suitable examples of the alcohols are methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec.-butyl alcohol, tert.-butyl alcohol, benzyl alcohol, furfuryl alcohol and tetrahydrofurfuryl alcohol.

The aliphatic amines used in accordance with the method of this invention may be primary, secondary and tertiary, or either monoamines or diamines. Furthermore, the aliphatic groups may be replaced by hydroxyl groups. Preferably, the aliphatic groups contain not more than 5 carbon atoms. Specific examples of the aliphatic amines that can be suitably used are methyl amine, dimethyl amine, trimethyl amine, monoethyl amine, diethyl amine, triethyl amine, n-propyl amine, isopropyl amibe, n-butyl amine, ethylene diamine, isobutyl amine, sec.-butyl amine, tertbutylamine, monoethanol amine, and isopropanol amine.

Of these compounds, n-butyl alcohol, iso-butyl alcoho], dioxane, acetone, and N,N-dimethyl formamide are especially suitable. Furthermore, these compounds may be used alone or in admixture of two or more, or further as admixture with water.

Where they are used as a mixture with water, the compounds are contained preferably in a total amount of at least 5 by weight based on the mixed vapor. The most suitable proportion of these compounds differs according to the types of the compounds used. Preferably, the proportion is not less than 5 by weight for acetone, not less than by weight for methyl amine, ethyl amine, and diethyl ketone, not less than by weight for n-propanol, iso-propanol, sec-butanol, tertbutanol, propyl amine and methyl ethyl ketone, not less than 30 by weight for n-butanol, iso-butanol and dimethyl amine, not less than 40 by weight for N,N- dimethyl formamide, furfuryl alcohol, dioxane and diethyl amine, not less than 50 by weight for N,N- dimethyl acetamide, methanol, ethanol, trimethyl amine, triethyl amine, ethylene diamine and isopropanol amine, and not less than 70 by weight for acetophenone, N,N-dimethyl sulfoxide, ethanol amine, and benzyl alcohol.

The mixed vapor of the above compounds and water can be easily prepared by mixing vapors of the compounds with steam, or heating an aqueous solution containing these compounds, or by blowing steam into the above compounds.

In the same way as in the conventional steaming process, the phenolic fibrous material to which a dye liquor has been applied is contacted with vapors of the above compounds or mixed vapors of water and the above compounds in a steaming chamber, for example, by feeding the vapors into a closed chamber in which the fibrous material is placed. The temperature of the vapors with which the fibrous material comes into contact differs according to the form, type and amount of the fibrous material used, the method of dyeing the material, the type of the dye used, the types of the above compounds, the amounts of these compounds in the mixed vapor, etc., but in general it is to 150C, preferably to 140C.

If the steaming temperature is too high, the fibers are swollen excessively during steaming. This contributes to increased diffusion of the dye, but on the other hand, causes the fixed dye to bleed out, thus reducing the dyeability. Furthermore, the tenacity of the fibers decreases, or the dye is decomposed during the treatment. If it is too low, no effective energy for fixing the dye to the material can be obtained. Accordingly, the optimum steaming temperature can be easily determined by those skilled in the art on a trial-and-error basis.

The time required for contacting the fibrous material with the vapors can be varied over a wide range according to various factors such as the form and type of the fibrous material, the type of the dye, or the amounts and types of the above compounds. Usually, it is 20 minutes to minutes, preferably about 30 to 90 minutes.

The fibrous material which has been steamed as described above is then subjected to a finishing treatment in accordance with a customary method. For example, a fibrous material dyed with a disperse dye and then steamed is washed with water, and then with an aqueous solution containing hydrosulfite, soda ash and a nonionic surface active agent, and finally dried. when the fibrous material is dyed with an azoic dye, cationic dye or vat dye and then steamed as described above, it is washed with water and then with an aqueous solution containing a non-ionic surface active agent, and finally dried.

The steaming treatment in accordance with the method of this invention promotes the diffusion of the dye adhered to the fibrous material into its interior, and makes it possible to obtain dyeings having uniform, deep fast colors. Furthermore, since the specific compounds used for the steaming treatment have high solubility in water, they do not give rise to difficulty of removal as in the case of the conventional carrier dyeing.

Furthermore, the method of the present invention makes it possible to color difficulty-dyeable phenolic fibrous materials in uniform deep colors with fastness characteristics without using any specific apparatus or costly chemicals. [t is therefore very useful for commercial application.

The vapor of the above specific compounds or the mixed vapors of the above compounds and water do not merely exhibit a swelling action on the fibers, but have an effect of neutralizing negative potential on the surfaces of the fibers and facilitating the diffusion of the dye into the fibers. This unique function and effect are clearly seen from the fact that when the phenolic fibrous material is colored by dip dyeing in a dye liquor containing methyl amine, dimethyl amine, ethyl amine, diethyl amine, ethylene diamine, methanol or ethanol, the dye is not at all fixed to the fibers, or even when a cloth to which the dye has been applied is heated in a bath of the above compounds, the dye is not fixed to the fibers.

This will be also clear from the fact that even when the fibrous material is treated in the gaseous phase with a mixed vapor of steam and phenol, cresol, cyclohexanol, aniline, an alkyl aniline, formamide, acetamide or acetic acid, the dye is not substantially fixed to the fibers, as will be shown by an example below.

The present invention will be further described by the following Examples in which all percentages are by EXAMPLE I A plain weave fabric prepared from monofilaments which were obtained by melt-spinning a novolak-type phenol resin and then curing the spun filaments with formaldehyde was dipped in a dye liquor of the following formulation, and then squeezed to an extent of 93 Formulation Sodium alginate (viscosity regulator) 0.5 Kg C.l. Disperse Violet l 30 Kg Water 69.5 Kg

Viscosity of the dye liquor 970 centipoises The fabric was then dried for minutes at 100C., and then treated for 30 minutes in a mixed vapor consisting of 50 ethylamine and 50 water and held at 140C. The fabric was then washed with water, and then with a reductive wash liquor consisting of 1 g/l of hydrosulfite, 1 g/l of soda ash, 1 g/l of Noigen HC (nonionic surface active agent, product of Daiichi Kogyo Seiyaku Kabushiki Kaisha), and water at 80C. for minutes. The material was then washed with water, and dried. The fabric was colored in a reddish deep violet.

The same cloth as used above which had been immersed in the same dye liquor was colored under the same conditions except that the ratio of the ethylamine to water was changed as shown in Table l. The results are shown in Table I.

Table 1 Dyed by dipping in a dye liquor consisting of 30 4: (based on the weight of the dye liquor) of ethylamine and 30 '7: (based on the weight of the material to he dyed) of a dye for 60 minutes at l30'C.

As is clear from the above results, when the content of ethylamine was 5 or more, dyeings colored deep and uniform were obtained.

When the material was dyed by dipping in a dye liquor containing ethylamine, the dye was not at all fixed to the material.

The dyeings had a light fastness of class 4, laundering fastness of class 4, and a rubbing fastness of class 5.

EXAMPLE 2 A tweed produced from a ply yarn composed of the same phenolic fibers as used in Example 1 was dipped in a dye liquor of the following formulation, and squeezed to an extent of Formulation Hydroxyethyl cellulose (viscosity regulator) 0.4 Kg

Foron Black S-ZBL (disperse dye,

Woduct of Sandoz AG) 25 Kg ater 74.6 Kg

Viscosity of the dye liquor I200 centipoises The tweed was then dried at C. for 5 minutes, and contacted with a mixed steam held at ll0C. and consisting of 50 of isopropanol amine and S0 of water for 60 minutes. The treated tweed was washed with water, and then with a reductive wash liquid consisting of l g/l of hydrosulfite, 0.5 g/l of soda ash, l g/l of a non-ionic surface active agent and water at 80C. for 20 minutes, followed by washing with water and drying.

The dyed cloth was colored in a bluish deep black.

The above procedure was repeated except that various amide compounds were used instead of the amine. The results are shown below in Table 2.

As is clear from the above results, when the tweed was dyed with a mixed vapor of N,N-dimethyl formamide-water or N,N-dimethyl acetamide-water, dyeings of deep and uniform colors were obtained, but when it EXAMPLE 3 A twill fabric produced from a ply yarn composed of the same phenolic fibers as used in Example 1 was printed with a paste-like dye liquor of the following formulation.

Formulation Diacryl Navy Blue BP (cationic dye, product of Mitsubishi Chemical Co. Ltd.)

Emulsion consisting of 50% of kerosene and 50% of water (viscosity regulator) Water Viscosity of the dye liquor 8000 centipoises The fabric was then dried at 90C., and then contacted with a mixed vapor held at 125C. and consisting of 50 25 of methanol and S of water for 60 minutes. The fabric was then washed with water, and washed with an aqueous solution containing 1 g/l of a non-ionic surface active agent for 3 minutes at 80C., followed by washing with water, and drying. The resultant fabric had a beautiful blue pattern.

The above procedure was repeated except that the mixed vapor contained the various alcohols shown in Table 3 in the proportions indicated. The results are shown in Table 3.

Table 3 Run Nos. Composition of the vapor (70) Dyeing density (K/S) l Methanol 50 11.52

Water 50 2 Ethanol 50 10.65

Water 50 3 n-Propanol 50 9.02

Water 50 4 n-Butanol 50 9.02

Water 50 5 Benzyl alcohol 50 9.02

Water 50 6 Water 100 0.29

(comparison) 7 n-Pentanol 50 0.47

Water 50 (comparison) 8 o-Phenyiphenol 20 0.26

Water 80 (comparison) 9 B-Naphthol 20 0.28

Water 80 (comparison) 10 N-methylaniline 0.28

Water B0 (comparison) 1 l Cyclohexanol 20 0.31

Water 80 (comparison) 12 Not steam-treated 0.26

As is clear from the above results, when the fabric was dyed using a mixed vapor of methanol-water, ethanol-water, n-propanol-water, n-butanol-water, or benzyl alcohol-water, dyeings of deep uniform colors were obtained. However, when the fabric was treated with steam alone or with a mixed vapor of n-pentanolwater, o-phenolphenyl-water, B-naphthol-water, N-

10 methylaniline-water, or cyclohexanol-water, the dye was not at all fixed to the fabric.

EXAMPLE 4 A plain weave fabric of the same structure as used in Example 1 was dipped in a dye liquor of the following formulation, and squeezed to an extent of Formulation Dianix Fast Brilliant Red BS (disperse dge, product of Mitsubishi hemical Co., Ltd.) 150 g 1,1 ,l-trichloroethane 850 g After application of the above dye liquor, the fabric was reductively washed for 3 minutes at 80C., washed with water, and dried. The dyed fabric was colored brilliant red.

The same fabric to which the dye was applied in the same way as above was treated under the same conditions as above with a vapor of dioxane, a vapor of diol, or a mixed vapor of either of these with water. The results are shown in Table 4.

Table 4 Run Dyeing density Nos. Composition of the vapor l5) 1 Dioxane 40 4.05

Water 60 2 Di oxane 4. 1 5 3 Water 100 0.26

(comparison) 4 Ethylene glycol 40 0.35 Water 60 (comparison) 5 Ethylene glycol 100 0.37

(comparison) 6 Diethylene glycol 40 Water (comparison) 60 7 Not treated with steam 0.26

EXAMPLE 5 A knitted fabric produced from a ply yarn composed of the same phenolic fibers as used in Example 1 was dipped in a dye liquor of the following formulation, and squeezed to an extent of 70 Formulation Carbox methyl cellulose Dianix as! Red 28 (disperse dye, product of Mitsubishi Chemical Co., Ltd.) Water I I Viscosity of the dye liquor 800 centrpoises 1 Bi ig After application of the above dye liquor, the fabric was contacted with a mixed vapor held at C. and consisting of 10 of acetone and 90 of water for 60 minutes while being rotated on a roll (without prior 1 l drying). The fabric was washed with water, and then washed with a reductive wash liquor consisting of 1 g/l of hydrosulfite, 0.5 g/l of soda ash, 1 g/l ofa non-ionic surface active agent and water at 80C. for 20 minutes,

Table 6-continued dye liquor) of dimethylfollowed by washing with water and drying. The resul- 5 l fi g i g g tant dyed fabric was colored red. bffi a ia d ye fc h titar isonl The above procedure was repeated using mixed va- 6 Aftefthe pp 5 pors of water with various ketones as shown in Table 5. above and sample was treated with The results are shown in Table 5. steam for 60 minutes (com l parison) Table 7 Aniline 50 0.29 Run D d t Water 50 yelng ens| y (com arison) Nos. Composition ofthe vapor (K/S) 8 Not s t eam-treated 0.23

l Acetone 10 4.05

Water 90 2 Diethyl ketone l0 l5 405 As 18 clear from the above results, when the material Water 90 was treated with a mixed vapor of dimethyl anine- 3 Methylethyl ketone 20 4 05 water, trimethyl amine-water, diethylamine-water or water 80 triethylamine-water, dyeings having uniform deep col- 4 Ammphenofle 70 20 ors were obtained. On the other hand, when the mate- Waler 30 rial was treated with a mixed vapor of aniline (an aro- 5 Water 100 0.37 matic amine) and water, the dye was not at all fixed to (comparison) 6 Not steam-treated 0.25 the matenal' Furthermore, when the material was dyed by dipping in a dye liquor containing dimethyl amine, the dye was As is clear from the above results when the fabric not at all fixed to the material. Furthermore, when a was treated with a mixed vapor of acetone-water, didye quot contaimmg (methyl zlmme was applied to a ethyl kemnbwater methylemyl ketonewater or cloth, and then it was treated with steam, the dye was acetophenone-water, dyeings of uniform deep colors fixed to the cloth could be Obtfllglet. However, \fyhe: it was treated with EXAMPLE 7 steam a one, t e e was not lxe at a y A twill fabric produced from a ply yarn composed of EXAMPLE 6 the same phenolic fibers as used in Example 1 was A curtain material composed of the same phenolic dipped in a dye liquor of the following formulation, and fibers as used in Example 1 was dipped in a dye liquor Squeezed to an extent of 63 of the following formulation, and squeezed to an extent of 50 Formulation Sodium alginate (viscosity 035 Kg regulator) Formulation 4O Foron Brown S-3RL (disperse Cibacet Green 56 (disperse l2 Kg Pmduc of Sand: AG) dye, product of Ciba Limited) f Kg water 88 Kg iscosity of the dye liquor 600 centipoises After application of the above dye liquor, the material 45 After the application the dye q the was dried at 100C for 5 minutes and the treated in dried at 100C. for 5 minutes, and then treated with a a mixed vapor held at 130C. and consisting of 30 of vapor held at Moccand conslstmg P 40 of dimethyl amine and 70 of waten The material was furfuryl alcohol and 60 of water for minutes. The washed with water and the washed with a reductive treated fabric was washed with water, and then washed wash liquor consisting of 1 g/l of hydrosulfite, 0.5 g/l of 3 reductive wash quot conslslmg l 8" of y' soda ash, l g/l of non-ionic surface active agent and drQsumte 1 g/l of Soda log/l of non'lofllc Surface water at 80C. for 20 minutes, followed by washing acme agem f f at 80 0 20 "mules, with water and drying. The resulting curtain material lowefj by washmg l and drymg- The resultant was Cobred in a beautiful green color fabric was colored in a reddish deep brown.

The above procedure was repeated except that mixed The above Procedure repeated l! h i vapors of water with various amines as shown in Table vapors of water and Vanous compounds mdlcated l" 6 were 56 The results are shown in Table Table 7 below were used. The results are shown in Table 7. Table 6 Table 7 Run Nos. Composition of the vapor (9b) Dyeing density (K/S) 60 Run Nos. Composition of the vapor Dyeing density (108) l Dlmethyl amine 30 10.13

Water l Furfuryl alcohol 40 l0.l5 2 Trimethyl amine 50 9.02 Water 60 Water 50 2 Acetic acid 50 0.47 3 Diethylamine 50 9.02 Water 50 Water 50 65 (com arison) 4 Triethylamine 50 9.02 3 Formic acid [0 0.45

Water 50 Water 90 5 Sam le dyed by dippin in a 0.50 (comparison) d e i uor consisting o 30% 4 Phenol 20 0.64 ase on the weight of the Water (comparison) 5 Not steam-treated 0.23

13 As is clear from the results shown above, when the fabric was treated with a mixed vapor of furfuryl alcoholwater, a dyeing of uniform deep color was obtained. On the other hand, when it was treated with a mixed vapor of acetic acid-water, formic acid-water or phenol-water, the dye was not at all fixed to the fabric.

EXAMPLE 8 A woven fabric produced from a ply yarn composed of the same phenolic fibers as used in Example 1 was dipped in a dye liquor of the following formulation, and squeezed to an extent of 57 Formulation Carboxymethyl cellulose (viscosity regulator) Dianix Brown R-E (disperse dye, product of Mitsubishi Chemical Co., Ltd.)

Water 20 Kg 79.8 Kg

in Table 8.

Table 8 Dyeing density Runs Composition of the vapor ('k) (K/S) Nos.

1 iso-Propanol 100 9.02

2 ISOPIO 50 9.66

Water pan S0 3 iso-Butanol 100 9.89

4 nso-Butauol 50 10.l3

Water 50 5 N,N-diethyl formamide I00 8.46

6 N,N-diethyl formamide 50 10. l 3

Water 50 7 Monomethyl amine I00 9.89

8 Monomethyl amine 50 9.23

Water 50 9 Ethylene diamine 100 9.02

l0 Ethylene diamine 50 9.44

Water 50 ll Dimethyl sulfoxide 50 9.23

Water 50. l 2 Dimethyl sulfoxide I00 9.44

13 Not stream-treated 0.26

As is clear from the results, when the fabric was treated with a vapor of isopropanol, isopropnaol-water, isobutanol, isobutanol-water, N,N-diethyl formamide, N,N-diethyl formamide-water, monomethyl amine, monoethyl amine-water, ethylene diamine, ethylene diamine-water, dimethyl sulfoxide, or dimethyl sulfox- 14 ide-water, dyeings having uniform deep colors were obtained.

EXAMPLE 9 A woven fabric produced from monofilaments composed of the same phenolic fibers as used in Example I was dipped in a dye liquor of the following formulation, and squeezed to an extent of Fonnulation TD 1200 (predi fi ing agent) 9 Kg TD Brilliant R (color developer, product of Daito Chemical Co., Ltd.) 2 Kg TD Bordeaux 25 (color developer, product of Daito Chemical Co., Ltd.) 4 Kg Sodium alginate l Kg Water 84 Kg After application of the above dye liquor, the fabric was dried for 10 minutes at C, and treated with a vapor of the compositions shown in Table 9 at C. for 60 minutes. Then, the treated fabric was washed with water, and then washed with an aqueous solution containing 1 gll of a nonionic surface active agent at 80C. for 20 minutes, followed by washing with water. Then, the fabric was treated with an aqueous solution containing 6 of 65 sulfuric acid and 3 of sodium nitrite for 30 minutes at 100C, followed by washing with warm water and cold water. The results are shown in Table 9.

Table 9 Dyeing density Run Nos. Composition of the vapor (I) (KIS) l N ,N-dimethyl formamide l 00 l l .52 2 N,N-dimethylformamide 80 10.93

Water 20 3 Water 100 0.25 4 Not steam-treated 0.23

As is clear from the above results, when the fabric was treated with a vapor of N,N-dimethyl formamide alone or a mixture of it with water, the fabric was dyed with good dyeability. However, when it was treated only with steam, the dye was not fixed to the fabric.

EXAMPLE 10 A woven fabric produced from a ply yarn composed of the same phenolic fibers as mentioned in Example I was printed with a dye liquor of the following formulation.

Formulation C. l. Vat Green 26 30 Kg Tragacanth gum l Kg Water 69 Kg Table Run Nos. Composition of the vapor (I) Dyeing density (K/S) l Furl'uryl alcohol 100 9.02

2 Tetrahydrofurfuryl alcoho 100 8.64 3 Monoethanol amine 100 9.23 44 Isopro anol amine 100 7.50 5 Methy ethyl ketone 100 6.60 6 Steam 100 0.26 7 Not steam-treated 0.23

As is clear from the results shown above, when the fabric was treated with a vapor of furfuryl alcohol, tetrahydrofurfuryl alcohol, monoethanol amine, isopropanol amine or methylethyl ketone, there were obtained printed materials colored in deep and fast colors.

What we claim is:

l. A method for coloring fibers or fibrous structures composed of phenolic resins, which comprises:

a. applying a dye liquor to said fibers or fibrous structures;

b. drying the resulting fiber or fibrous structures; and

c. contacting the dried fiber or fibrous structures with a mixed vapor of water and at least 5% by weight,

16 based on the total weight of the mixed vapor, of benzyl alcohol.

2. The method of claim I wherein said mixed vapor is maintained at a temperature of C. to 150C.

3. The method of claim 1 wherein said fibers or iibrous structures are contacted with said mixed vapor for 20 to minutes.

4. The method of claim 1 wherein said dye liquor is a solution, emulsion or paste containing a dye.

5. The method of claim I wherein said dye liquor contains a disperse dye, azoic dye, cationic dye or vat dye.

6. The method of claim 1 wherein the dye liquor is applied by padding or printing.

7. A method for printing fibrous structures composed of a phenolic resins, which comprises:

a. applying an aqueous paste containing a dye to said fibrous structures;

b. drying the resulting fibrous structures; and

c. contacting the dried fibrous structures with a mixed vapor of water and at least 5% by weight, based on the total weight of the mixed vapor, of benzyl alcohol at a temperature of 100C. to C. for 20 to 120 minutes. 

1. A METHOD FOR COLORING FIBERS OR FIBROUS STRUCTURES COMPOSED OF PHENOLIC RESINS, WHICH COMPRISES: A. APPLYING A DYE LIQUOR TO SAID FIBERS OR FIBROUS STRUCTURES; B. DRYING THE RESULTING FIBER OF FIBROUS STRUCTURES; AND C. CONTACTING THE DRIED FIBER OR FIBROUS STRUCTURES WITH A MIXED VAPOR OF WATER AND AT LEAST 5% BY WEIGHT, BASED ON THE TOTAL WEIGHT OF THE MIXED VAPOR, OF BENZYL ALCOHOL.
 2. The method of claim 1 wherein said mixed vapor is maintained at a temperature of 100*C. to 150*C.
 3. The method of claim 1 wherein said fibers or fibrous structures are contacted with said mixed vapor for 20 to 120 minutes.
 4. The method of claim 1 wherein said dye liquor is a solution, emulsion or paste containing a dye.
 5. The method of claim 1 wherein said dye liquor contains a disperse dye, azoic dye, cationic dye or vat dye.
 6. The method of claim 1 wherein the dye liquor is applied by padding or printing.
 7. A method for printing fibrous structures composed of a phenolic resins, which comprises: a. applying an aqueous paste containing a dye to said fibrous structures; b. drying the resulting fibrous structures; and c. contacting the dried fibrous structures with a mixed vapor of water and at least 5% by weight, based on the total weight of the mixed vapor, of benzyl alcohol at a temperature of 100*C. to 150*C. for 20 to 120 minutes. 